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951.
The 9-[(E)-1,2-dichloroviny1]carbazole is a starting material for synthesis of 9-ethynyl-carbazole [1], which in term is monomer for preparation of photoconductive polymers [2]. Dichlorovinylation of carbazole in a solid-liquid two phase system in the presence of crown and cryptand catalysts has been studied. Application of the Phase Transfer Catalysis in the nonaqueous system increases yield of 9-[(E)-1,2-dichloroviny1]carbazole in comparison to the methods based on liquid-liquid system with benzyltriethylammonium chloride (TEBA) or dimethylsulfoxide (DMSO) as catalysts. 相似文献
952.
Several solutions have been developed to avoid the troublesome di- and polyalkylation encountered in ketone enolate alkylations1, including use of the covalent Li enolate, or “additives” to tighten the metal-oxygen bond (M = Si2,3,4, Sn5,6, Al6, B7,8,9). 相似文献
953.
A. D. Milov Y. D. Tsvetkov M. De Zotti C. Prinzivalli B. Biondi F. Formaggio C. Toniolo M. Gobbo 《Journal of Structural Chemistry》2013,54(1):73-85
The X band PELDOR spectroscopy was used to investigate the magnetic dipole-dipole interactions in glassy solutions of nitroxide mono-labeled tylopeptin B and heptaibin peptaibiotics at 77 K. Specifically, a study was performed of the tylopeptin B peptides labeled at either position 3, 8, or 13, denoted as T3, T8, and T13, respectively. The heptaibin analogs labeled at either position 2 or 14, denoted as H2 and H14, respectively, were also investigated. It was shown that in frozen glassy peptide solutions in methanol, the spin labels are randomly distributed over the solvent volume. This result points to the absence of specific dipolar interactions between the peptides under these conditions. However, peptide aggregation was detected in weakly polar methanol/toluene environments. To study the properties of the resulting aggregates, we examined the depth of modulation for the PELDOR traces as a function of the concentration of the peptides in solution and the distances between the spin labels in the aggregates. Based on the concentration dependencies, the number of peptide molecules in the aggregates was estimated. We find that this value ranges from 2 to 3, depending on the position of the spin label in the peptide sequence. The combined analysis of the distance spectra and the number of peptide molecules in the aggregates allows us to suggest that dimer formation is the prevailing mode of self-association. In the case of spin-labeled tylopeptin B, the molecules in the dimer are head-to-head oriented. In addition, the distance spectra of the aggregates show that the C-termini of the molecules in the tylopeptin B dimer are more mobile than the Ntermini. This phenomenon leads to an increase in the spread of the distances between the nitroxides as the label position is approaching the peptide C-terminus. For heptaibin, we show that two forms of dimerization (head-to-head and head-to-tail) occur. Finally, in addition to dimers, aggregates containing 3 or 4 peptide molecules, which give broad lines in the distance spectra, are seen in solution. 相似文献
954.
Tomas Bertok Pavol Gemeiner Milan Mikula Peter Gemeiner Jan Tkac 《Mikrochimica acta》2013,180(1-2):151-159
We report on an ultrasensitive label-free lectin-based impedimetric biosensor for the determination of the sialylated glycoproteins fetuin and asialofetuin. A sialic acid binding agglutinin from Sambucus nigra I was covalently immobilised on a mixed self-assembled monolayer (SAM) consisting of 11-mercaptoundecanoic acid and 6-mercaptohexanol. Poly(vinyl alcohol) was used as a blocking agent. The sensor layer was characterised by atomic force microscopy, electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy. The biosensor exhibits a linear range that spans 7 orders of magnitude for both glycoproteins, with a detection limit as low as 0.33 fM for fetuin and 0.54 fM for asialofetuin. We also show, by making control experiments with oxidised asialofetuin, that the biosensor is capable of quantitatively detecting changes in the fraction of sialic acid on glycoproteins. We conclude that this work lays a solid foundation for future applications of such a biosensor in terms of the diagnosis of diseases such as chronic inflammatory rheumatoid arthritis, genetic disorders and cancer, all of which are associated with aberrant glycosylation of protein biomarkers. Figure
Key aspects of the biosensor: 1) mixed SAM formation, 2) immobilisation of lectin & blocking and 3) a glycoprotein recognition. 相似文献
955.
The racemic mixtures of 1-aryloxy-3-nitrato-2-propanols and 1-aryloxy-3-azido-2-propanols were resolved with moderate selectivity by the lipase-mediated acylation with vinyl acetate. The effects of the nature, position, and spatial requirements of the phenyl-ring substituents on the resolution degree were investigated. 相似文献
956.
957.
958.
Christopher G. Mayne Jan Saam Klaus Schulten Emad Tajkhorshid James C. Gumbart 《Journal of computational chemistry》2013,34(32):2757-2770
The inability to rapidly generate accurate and robust parameters for novel chemical matter continues to severely limit the application of molecular dynamics simulations to many biological systems of interest, especially in fields such as drug discovery. Although the release of generalized versions of common classical force fields, for example, General Amber Force Field and CHARMM General Force Field, have posited guidelines for parameterization of small molecules, many technical challenges remain that have hampered their wide‐scale extension. The Force Field Toolkit (ffTK), described herein, minimizes common barriers to ligand parameterization through algorithm and method development, automation of tedious and error‐prone tasks, and graphical user interface design. Distributed as a VMD plugin, ffTK facilitates the traversal of a clear and organized workflow resulting in a complete set of CHARMM‐compatible parameters. A variety of tools are provided to generate quantum mechanical target data, setup multidimensional optimization routines, and analyze parameter performance. Parameters developed for a small test set of molecules using ffTK were comparable to existing CGenFF parameters in their ability to reproduce experimentally measured values for pure‐solvent properties (<15% error from experiment) and free energy of solvation (±0.5 kcal/mol from experiment). © 2013 Wiley Periodicals, Inc. 相似文献
959.
Jan Kameník Henrieta Dulaiova Ferdinand Šebesta Kamila Šťastná 《Journal of Radioanalytical and Nuclear Chemistry》2013,296(2):841-846
The method developed for cesium concentration from large freshwater samples was tested and adapted for analysis of cesium radionuclides in seawater. Concentration of dissolved forms of cesium in large seawater samples (about 100 L) was performed using composite absorbers AMP-PAN and KNiFC-PAN with ammonium molybdophosphate and potassium–nickel hexacyanoferrate(II) as active components, respectively, and polyacrylonitrile as a binding polymer. A specially designed chromatography column with bed volume (BV) 25 mL allowed fast flow rates of seawater (up to 1,200 BV h?1). The recovery yields were determined by ICP-MS analysis of stable cesium added to seawater sample. Both absorbers proved usability for cesium concentration from large seawater samples. KNiFC-PAN material was slightly more effective in cesium concentration from acidified seawater (recovery yield around 93 % for 700 BV h?1). This material showed similar efficiency in cesium concentration also from natural seawater. The activity concentrations of 137Cs determined in seawater from the central Pacific Ocean were 1.5 ± 0.1 and 1.4 ± 0.1 Bq m?3 for an offshore (January 2012) and a coastal (February 2012) locality, respectively, 134Cs activities were below detection limit (<0.2 Bq m?3). 相似文献
960.
Ivana Krausová Jan Kučera Ivo Světlík 《Journal of Radioanalytical and Nuclear Chemistry》2013,295(3):2043-2048
Neutron activation analysis (NAA) was used to determine 129I and the 129I/127I ratio in bovine thyroid, moss, and river sediment samples collected in the vicinity of the Temelín nuclear power plant (NPP) in south Bohemia. The NAA procedures comprised pre-irradiation separation of 129I by combustion of the samples in the stream of oxygen at 1,000 °C and trapping the liberated iodine in a LiOH/(NH4)2SO3 solution. Post-irradiation separation of 130I produced by the reaction 129I(n,γ)130I was carried out by extraction of elementary iodine with chloroform followed by precipitation of PdI2. Nondestructive, epithermal NAA was used to determine 127I employing the 127I(n,γ)128I reaction. The results showed that mean values of 129I and the 129I/127I ratio in the bovine thyroids varied from 22 to 61 mBq kg?1 (dry mass) and 2.8 × 10?9 to 5.4 × 10?9, respectively. These values are close to the lower end of results reported from various regions non-polluted with 129I. No significant differences were found between 129I concentrations and the 129I/127I ratios in the bovine thyroids collected prior to the start and after several years of operation of the NPP. The mean value and standard deviation of 129I in mBq kg?1, dry mass and the 129I/127I ratio in moss Pleurozium schreberi were 23 ± 16 and 2.3 × 10?9, respectively, whereas values of 129I in the river sediments were below 8–10 mBq kg?1 (dry mass) after several years of the NPP operation. 相似文献